JP5771358B2 - Method for producing regenerated Fischer-Tropsch synthesis catalyst and method for producing hydrocarbon - Google Patents
Method for producing regenerated Fischer-Tropsch synthesis catalyst and method for producing hydrocarbon Download PDFInfo
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- JP5771358B2 JP5771358B2 JP2010049633A JP2010049633A JP5771358B2 JP 5771358 B2 JP5771358 B2 JP 5771358B2 JP 2010049633 A JP2010049633 A JP 2010049633A JP 2010049633 A JP2010049633 A JP 2010049633A JP 5771358 B2 JP5771358 B2 JP 5771358B2
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- synthesis
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- synthesis catalyst
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- 239000003054 catalyst Substances 0.000 title claims description 339
- 238000003786 synthesis reaction Methods 0.000 title claims description 333
- 230000015572 biosynthetic process Effects 0.000 title claims description 210
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229930195733 hydrocarbon Natural products 0.000 title claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 title description 14
- 230000000694 effects Effects 0.000 claims description 113
- 238000006243 chemical reaction Methods 0.000 claims description 70
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 52
- 239000007789 gas Substances 0.000 claims description 50
- 230000009467 reduction Effects 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 44
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 40
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000010025 steaming Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000011148 porous material Substances 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 230000000875 corresponding effect Effects 0.000 description 51
- 230000014759 maintenance of location Effects 0.000 description 47
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 34
- 238000011084 recovery Methods 0.000 description 28
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- 229910004298 SiO 2 Inorganic materials 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 22
- 238000002360 preparation method Methods 0.000 description 22
- 238000011068 loading method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- 150000003755 zirconium compounds Chemical class 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- BDSSZTXPZHIYHM-UHFFFAOYSA-N 2-phenoxypropanoyl chloride Chemical compound ClC(=O)C(C)OC1=CC=CC=C1 BDSSZTXPZHIYHM-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- LYTNHSCLZRMKON-UHFFFAOYSA-L oxygen(2-);zirconium(4+);diacetate Chemical compound [O-2].[Zr+4].CC([O-])=O.CC([O-])=O LYTNHSCLZRMKON-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003304 ruthenium compounds Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- TZWGXFOSKIHUPW-UHFFFAOYSA-L cobalt(2+);propanoate Chemical compound [Co+2].CCC([O-])=O.CCC([O-])=O TZWGXFOSKIHUPW-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- -1 organic acid salt Chemical class 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- PFXYQVJESZAMSV-UHFFFAOYSA-K zirconium(iii) chloride Chemical compound Cl[Zr](Cl)Cl PFXYQVJESZAMSV-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/96—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/332—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the iron-group
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、再生フィッシャー・トロプシュ合成触媒の製造方法、及び該製造方法により製造された触媒を用いる炭化水素の製造方法に関する。 The present invention relates to a method for producing a regenerated Fischer-Tropsch synthesis catalyst, and a method for producing hydrocarbons using the catalyst produced by the production method.
近年、ガソリンや軽油のような液体燃料に含まれる硫黄分等の環境負荷物質に対する規制が急速に厳しくなってきている。そのため、硫黄分や芳香族炭化水素の含有量が低い環境にやさしいクリーンな液体燃料の製造が不可欠となっている。このようなクリーン燃料の製造方法の一つとして、一酸化炭素を水素で還元する、いわゆるフィッシャー・トロプシュ合成法（以下、「ＦＴ合成法」ということもある。）が挙げられる。ＦＴ合成法により、パラフィン炭化水素に富み、かつ硫黄分を含まない液体燃料基材を製造することができると共に、ワックスも製造することができる。そして、このワックスは水素化分解により中間留分（灯油や軽油などの燃料基材）へと変換することができる。 In recent years, regulations on environmentally harmful substances such as sulfur contained in liquid fuels such as gasoline and light oil have been rapidly tightened. Therefore, it is indispensable to produce an environment-friendly clean liquid fuel with a low content of sulfur and aromatic hydrocarbons. One method for producing such a clean fuel is a so-called Fischer-Tropsch synthesis method (hereinafter also referred to as “FT synthesis method”) in which carbon monoxide is reduced with hydrogen. By the FT synthesis method, it is possible to produce a liquid fuel base material rich in paraffin hydrocarbons and not containing sulfur, and wax can also be produced. This wax can be converted into middle distillates (fuel base materials such as kerosene and light oil) by hydrocracking.
フィッシャー・トロプシュ合成反応（以下、「ＦＴ合成反応」ということもある。）に使用される触媒であるフィッシャー・トロプシュ合成触媒（以下、「ＦＴ合成触媒」ということもある。）は、一般にシリカやアルミナなどの担体上に、鉄、コバルト、ルテニウムなどの活性金属を担持した触媒である（例えば特許文献１を参照）。また、ＦＴ合成触媒においては、上記活性金属に加えて第２の金属を使用することにより、触媒性能が向上することが報告されている（例えば特許文献２を参照）。第２の金属としては、ナトリウム、マグネシウム、リチウム、ジルコニウム、ハフニウムなどが挙げられ、一酸化炭素の転化率向上またはワックス生成量の指標となる連鎖成長確率の増加など、目的に応じて適宜使用されている。ＦＴ合成触媒の実際の使用に際しては、触媒の活性低下を最小限に留める観点からも、上記第２の金属の組み合わせ使用が検討されている。 A Fischer-Tropsch synthesis catalyst (hereinafter also referred to as “FT synthesis catalyst”), which is a catalyst used in a Fischer-Tropsch synthesis reaction (hereinafter also referred to as “FT synthesis reaction”), is generally a silica or A catalyst in which an active metal such as iron, cobalt, or ruthenium is supported on a support such as alumina (see, for example, Patent Document 1). In addition, in the FT synthesis catalyst, it is reported that the catalyst performance is improved by using a second metal in addition to the active metal (see, for example, Patent Document 2). Examples of the second metal include sodium, magnesium, lithium, zirconium, hafnium, and the like. The second metal is appropriately used according to the purpose, such as an improvement in the conversion rate of carbon monoxide or an increase in chain growth probability as an index of the amount of wax produced. ing. In actual use of the FT synthesis catalyst, the combined use of the second metal has been studied from the viewpoint of minimizing the decrease in the activity of the catalyst.
実用のＦＴ合成触媒に要求される性能としては、触媒活性、生成物選択性、触媒寿命が主に挙げられる。このうち触媒寿命を短くする触媒劣化要因については、反応中の炭素質析出（例えば非特許文献１を参照）、活性金属の酸化劣化（例えば非特許文献２を参照）、活性金属と担体との化合物生成（例えば非特許文献３を参照）など研究例が多数ある。その一方で、一旦劣化した触媒そのものの活性を復活させることは依然として困難であり、新触媒を装置に追加投入することで活性劣化分を補填せざるを得ないのが現状である。この方法では、高価な触媒の追加投入が必要になるためコストアップとなるだけでなく、結果的に廃棄物となる使用済み触媒の量が増えることも問題となっていた。 The performance required for a practical FT synthesis catalyst mainly includes catalyst activity, product selectivity, and catalyst life. Among these, the catalyst deterioration factors that shorten the catalyst life include carbonaceous precipitation during the reaction (for example, see Non-Patent Document 1), oxidative deterioration of the active metal (for example, see Non-Patent Document 2), active metal and support There are many research examples, such as compound production (for example, refer nonpatent literature 3). On the other hand, it is still difficult to restore the activity of the once deteriorated catalyst itself, and it is unavoidable to compensate for the activity deterioration by additionally introducing a new catalyst into the apparatus. In this method, since it is necessary to add an expensive catalyst, not only the cost is increased, but also the amount of the used catalyst which becomes waste as a result increases.
以上のような状況から、ＦＴ合成反応に使用され活性が低下したＦＴ合成触媒を、再度使用可能な水準まで再生する、簡易な方法の開発が望まれていた。 In view of the above situation, there has been a demand for the development of a simple method for regenerating the FT synthesis catalyst used in the FT synthesis reaction and having reduced activity to a reusable level.
本発明者らは、上記の問題に鑑み、鋭意研究を重ねた結果、劣化したＦＴ合成触媒を特定の条件下に水蒸気にて処理することにより、活性を回復させることができることを見出し、本発明を完成するに至ったものである。 In view of the above problems, the present inventors have conducted extensive research and found that the activity can be recovered by treating the deteriorated FT synthesis catalyst with water vapor under specific conditions. Has been completed.
すなわち、本発明は、フィッシャー・トロプシュ合成反応に使用した使用済み触媒を再生して得られる再生フィッシャー・トロプシュ合成触媒の製造方法であって、シリカを含む担体にコバルトが担持され、初期一酸化炭素転化率で表される活性が、相当する未使用の触媒の当該活性を基準として４０〜９５％である上記使用済み触媒を、大気圧〜５ＭＰａの圧力、１５０〜３５０℃の温度にて、１〜３０体積％の水蒸気及び不活性ガスを含む混合ガスに接触させるスチーミング工程を備え、上記シリカを含む担体は、窒素吸着法による平均細孔径が４〜２５ｎｍであり、シリカを含む担体が、更に触媒の質量を基準として１〜１０質量％の酸化ジルコニウムを含む、ことを特徴とする再生フィッシャー・トロプシュ合成触媒の製造方法を提供する。 That is, the present invention is a manufacturing method of reproducing a Fischer-Tropsch synthesis catalyst obtained by reproducing the spent catalyst used in the Fischer-Tropsch synthesis reaction, cobalt is supported on a carrier containing by silica, the initial one The used catalyst having an activity represented by carbon oxide conversion of 40 to 95% based on the activity of the corresponding unused catalyst is measured at a pressure of atmospheric pressure to 5 MPa and a temperature of 150 to 350 ° C. , comprising a steaming step of contacting the mixed gas containing 30 vol% of water vapor and inert gas, carrier comprising the silica has an average pore diameter by nitrogen adsorption method Ri 4~25nm der, including silica carrier further comprises 1 to 10 wt% of zirconium oxide, based on the weight of the catalyst, a method for manufacturing a reproduction Fischer-Tropsch synthesis catalyst, wherein the Hisage To.
本発明の再生フィッシャー・トロプシュ合成触媒の製造方法は、上記スチーミング工程を経て得られた触媒を、分子状水素又は一酸化炭素を含む気体中で還元する還元工程を更に備えることが好ましい。 The method for producing a regenerated Fischer-Tropsch synthesis catalyst of the present invention preferably further comprises a reduction step of reducing the catalyst obtained through the steaming step in a gas containing molecular hydrogen or carbon monoxide.
また、上記シリカを含む担体が、更に触媒の質量を基準として１〜１０質量％の酸化ジルコニウムを含むことが好ましい。 Moreover, it is preferable that the said support | carrier containing a silica contains 1-10 mass% zirconium oxide further on the basis of the mass of a catalyst.
また、上記スチーミング工程を含む再生フィッシャー・トロプシュ合成触媒を製造するための全工程を、フィッシャー・トロプシュ合成反応装置と接続された再生装置内において実施することが好ましい。 Moreover, it is preferable that all the steps for producing the regenerated Fischer-Tropsch synthesis catalyst including the steaming step are carried out in a regenerator connected to the Fischer-Tropsch synthesis reactor.
更に、本発明は、上記の方法により製造された再生フィッシャー・トロプシュ合成触媒の存在下に、一酸化炭素及び分子状水素を含む原料をフィッシャー・トロプシュ合成反応に供することを特徴とする炭化水素の製造方法を提供する。 Furthermore, the present invention provides a hydrocarbon comprising a raw material containing carbon monoxide and molecular hydrogen in a Fischer-Tropsch synthesis reaction in the presence of a regenerated Fischer-Tropsch synthesis catalyst produced by the above method. A manufacturing method is provided.
本発明によれば、ＦＴ合成反応に使用され活性が低下したＦＴ合成触媒を簡易な方法により再度使用可能な水準まで再生する再生ＦＴ合成触媒の製造方法、及び該方法により製造された再生ＦＴ合成触媒を使用する炭化水素の製造方法が提供される。 According to the present invention, a method for producing a regenerated FT synthesis catalyst that is used in an FT synthesis reaction and regenerates an FT synthesis catalyst having reduced activity to a reusable level by a simple method, and a regenerated FT synthesis produced by the method. A method for producing hydrocarbons using a catalyst is provided.
以下、本発明について、好ましい実施形態に沿って詳細に説明する。 Hereinafter, the present invention will be described in detail according to preferred embodiments.
まず、本発明の再生ＦＴ合成触媒の製造方法において使用する使用済みＦＴ合成触媒について、未使用の段階の当該触媒の製造方法を述べることにより説明する。 First, the used FT synthesis catalyst used in the method for producing a regenerated FT synthesis catalyst of the present invention will be described by describing a method for producing the catalyst at an unused stage.
上記触媒を構成する担体は、シリカを含むものである。シリカを含む担体としては、シリカの他に、少量のアルミナ、チタニア、マグネシアなどの多孔性無機酸化物や、ナトリウム、マグネシウム、リチウム、ジルコニウム、ハフニウム等の金属成分を含むシリカを挙げることができる。 The carrier that constitutes the catalyst contains silica. Examples of the carrier containing silica include a small amount of porous inorganic oxides such as alumina, titania and magnesia, and silica containing metal components such as sodium, magnesium, lithium, zirconium and hafnium.
上記シリカを含む担体の性状に特に制限はないが、窒素吸着法で測定される比表面積が５０〜８００ｍ２／ｇであることが好ましく、１５０〜５００ｍ２／ｇであることがより好ましい。比表面積が５０ｍ２／ｇ未満である場合は、活性金属が凝集して触媒が低活性となるため好ましくない。一方で、比表面積が８００ｍ２／ｇより大きい場合は、コーキングによる触媒活性低下速度が大きくなるため好ましくない。 There is no particular limitation on the nature of the support containing the silica, it is preferable that the specific surface area determined by nitrogen adsorption method is 50 to 800 m 2 / g, more preferably 150~500m 2 / g. When the specific surface area is less than 50 m 2 / g, the active metal aggregates and the catalyst becomes less active, which is not preferable. On the other hand, when the specific surface area is larger than 800 m 2 / g, the rate of decrease in catalytic activity due to coking increases, which is not preferable.
また、本発明におけるシリカを含む担体の窒素吸着法による平均細孔径は、４〜２５ｎｍであり、８〜２２ｎｍであることが好ましい。平均細孔径が４ｎｍより小さい場合は、活性金属が担体細孔外に過度に凝集するため、初期の段階から活性が低下する傾向があるため好ましくない。一方、平均細孔径が２５ｎｍより大きな場合も、比表面積が低いことから所定量の活性金属を十分分散した状態で担持することが困難である。 Moreover, the average pore diameter by the nitrogen adsorption method of the support | carrier containing the silica in this invention is 4-25 nm, and it is preferable that it is 8-22 nm. When the average pore diameter is smaller than 4 nm, the active metal is excessively aggregated outside the support pores, so that the activity tends to decrease from the initial stage, which is not preferable. On the other hand, even when the average pore diameter is larger than 25 nm, it is difficult to carry a predetermined amount of active metal in a sufficiently dispersed state because the specific surface area is low.
担体の形状については、特に制限はないが、実用性を考慮すると、一般に石油精製や石油化学の実装置で使用されている球状、円柱状および三つ葉型・四葉型などの断面をもつ異形円柱状などの形状が好ましい。また、その粒子径についても特に制限はないが、実用性から１μｍ〜１０ｍｍであることが好ましい。なお、ＦＴ合成反応に好ましく用いられるスラリー床反応装置を使用してＦＴ合成反応を行う場合には、触媒粒子の流動性を確保する観点から、担体の形状は球状が好ましく、その粒子径は１０〜３００μｍ程度が好ましく、３０〜１５０μｍ程度がより好ましい。 The shape of the carrier is not particularly limited, but in consideration of practicality, it is generally a spherical, cylindrical shape, or a modified cylindrical shape having a cross section such as a three-leaf type or a four-leaf type, which is generally used in actual equipment for petroleum refining or petrochemistry. A shape such as is preferable. Moreover, there is no restriction | limiting in particular also about the particle diameter, However, It is preferable that it is 1 micrometer-10 mm from practicality. In addition, when performing FT synthesis reaction using the slurry bed reaction apparatus preferably used for FT synthesis reaction, the shape of a support | carrier is preferable from a viewpoint of ensuring the fluidity | liquidity of a catalyst particle, and the particle diameter is 10 About -300 micrometers is preferable and about 30-150 micrometers is more preferable.
上記シリカを含む担体は、活性の向上及び使用中の経時的な活性の低下の抑制の観点から、更にジルコニウムを含むことが好ましい。ジルコニウムの含有量は、触媒の質量を基準として、酸化ジルコニウムとして１〜１０質量％であることが好ましく、２〜８質量％であることがより好ましい。上記含有量が１質量％未満である場合には、ジルコニウムを含むことによる上記効果を発揮しにくい傾向にあり、また、１０質量％を超える場合には、担体の細孔容積が低下する傾向にあるため好ましくない。なお、ジルコニウムの担持方法としては特に制限はなく、Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ法に代表される含浸法を用いることができる。担持に使用するジルコニウム化合物としては、硫酸ジルコニール、酢酸ジルコニール、炭酸ジルコニールアンモニウム、三塩化ジルコニウムなどを用いることができ、炭酸ジルコニールアンモニウムおよび酢酸ジルコニールがより好ましい。 It is preferable that the carrier containing silica further contains zirconium from the viewpoints of improvement in activity and suppression of decrease in activity over time during use. The content of zirconium is preferably 1 to 10% by mass and more preferably 2 to 8% by mass as zirconium oxide based on the mass of the catalyst. When the content is less than 1% by mass, the above effect due to the inclusion of zirconium tends to be difficult to exert. When the content exceeds 10% by mass, the pore volume of the support tends to decrease. This is not preferable. In addition, there is no restriction | limiting in particular as a loading method of a zirconium, The impregnation method represented by the Incipient Wetness method can be used. Zirconyl sulfate, zirconyl acetate, zirconyl ammonium carbonate, zirconium trichloride and the like can be used as the zirconium compound used for loading, and zirconyl ammonium carbonate and zirconyl acetate are more preferable.
ジルコニウム化合物の担持後、含浸溶液と担体（ジルコニウム化合物を担持したシリカ）とを分離し、その後、担体を乾燥する。乾燥方法は特に制限されるものではなく、例えば、空気中での加熱乾燥や減圧下での脱気乾燥を挙げることができる。乾燥は、通常、温度１００〜２００℃、好ましくは１１０〜１３０℃で、２〜２４時間、好ましくは５〜１２時間行う。 After supporting the zirconium compound, the impregnation solution and the support (silica supporting the zirconium compound) are separated, and then the support is dried. The drying method is not particularly limited, and examples thereof include heat drying in air and deaeration drying under reduced pressure. The drying is usually performed at a temperature of 100 to 200 ° C., preferably 110 to 130 ° C., for 2 to 24 hours, preferably 5 to 12 hours.
乾燥後、ジルコニウム化合物が担持された担体を焼成し、ジルコニウム化合物を酸化物へと変換する。焼成の条件は特に制限されるものではないが、通常、空気雰囲気下に３４０〜６００℃、好ましくは４００〜４５０℃で、１〜５時間行うことができる。以上のようにして、酸化ジルコニウムが担持されたシリカ担体が得られる。 After drying, the support on which the zirconium compound is supported is fired to convert the zirconium compound into an oxide. The firing conditions are not particularly limited, but are usually 340 to 600 ° C., preferably 400 to 450 ° C., for 1 to 5 hours in an air atmosphere. As described above, a silica carrier carrying zirconium oxide is obtained.
次に、上記のようにして得られた担体に活性金属を含む化合物を担持する。活性金属としては、コバルト及び／又はルテニウムが一酸化炭素転換活性、生成物選択性の観点から好ましい。 Next, a compound containing an active metal is supported on the carrier obtained as described above. As the active metal, cobalt and / or ruthenium are preferable from the viewpoint of carbon monoxide conversion activity and product selectivity.
コバルトル及び／又はルテニウムを担持する際に使用するこれら金属元素を含む化合物としては特に限定されることはなく、これら金属の鉱酸あるいは有機酸の塩又は錯体を使用することができる。例えば、コバルト化合物としては、硝酸コバルト、塩化コバルト、蟻酸コバルト、酢酸コバルト、プロピオン酸コバルト、コバルトアセチルアセトナートなどを挙げることができる。ルテニウム化合物としては、塩化ルテニウム、硝酸ルテニウム、テトラオキソルテニウム酸塩等が挙げられる。 The compound containing these metal elements used for supporting cobalt and / or ruthenium is not particularly limited, and a mineral acid or organic acid salt or complex of these metals can be used. For example, examples of the cobalt compound include cobalt nitrate, cobalt chloride, cobalt formate, cobalt acetate, cobalt propionate, and cobalt acetylacetonate. Examples of the ruthenium compound include ruthenium chloride, ruthenium nitrate, and tetraoxoruthenate.
コバルト及び／又はルテニウム化合物の担持量に特に制限はないが、一般には触媒の質量を基準として、金属原子として３〜５０質量％、好ましくは１０〜３０質量％である。担持量が３質量％未満の場合には活性が不十分となる傾向にあり、５０質量％を超える場合には、活性金属の凝集が起こり、活性が低下する傾向にある。 Although there is no restriction | limiting in particular in the load of a cobalt and / or ruthenium compound, Generally it is 3-50 mass% as a metal atom on the basis of the mass of a catalyst, Preferably it is 10-30 mass%. When the supported amount is less than 3% by mass, the activity tends to be insufficient, and when it exceeds 50% by mass, the active metal tends to aggregate and the activity tends to decrease.
活性金属化合物の担持方法としては特に制限はなく、Ｉｎｃｉｐｉｅｎｔ Ｗｅｔｎｅｓｓ法に代表される含浸法を用いることができる。 There is no restriction | limiting in particular as a loading method of an active metal compound, The impregnation method represented by the Incipient Wetness method can be used.
活性金属化合物を担持した後、通常、温度１００〜２００℃、好ましくは１１０〜１３０℃で、２〜２４時間、好ましくは５〜１０時間乾燥し、次いで、空気雰囲気下に３４０〜６００℃、好ましくは４００〜４５０℃で、１〜５時間焼成を行い、活性金属化合物を酸化物へと変換することによりＦＴ合成触媒が得られる。 After supporting the active metal compound, it is usually dried at a temperature of 100 to 200 ° C., preferably 110 to 130 ° C. for 2 to 24 hours, preferably 5 to 10 hours, and then 340 to 600 ° C. in an air atmosphere, preferably Is calcined at 400 to 450 ° C. for 1 to 5 hours, and an active metal compound is converted into an oxide to obtain an FT synthesis catalyst.
上記ＦＴ合成触媒は、ＦＴ合成反応に対する十分な活性を付与するために、一般的には分子状水素を含む雰囲気下に還元を行ない、活性金属を酸化物から金属へと変換することにより活性化した後、ＦＴ合成反応に供することが一般的である。 The above FT synthesis catalyst is generally activated by converting it from an oxide to a metal by performing reduction under an atmosphere containing molecular hydrogen in order to impart sufficient activity to the FT synthesis reaction. Then, it is common to use for FT synthesis reaction.
なお、上記触媒の活性化が、ＦＴ合成法により炭化水素を製造する設備あるいはそれに付属する設備において行なわれる場合は、活性化された触媒はそのままＦＴ合成反応に供される。一方、例えば炭化水素の製造設備と離れた触媒製造設備において上記活性化が行われる場合には、移送時等における空気との接触により触媒が失活することを防止するために、安定化処理が施されてから出荷されることが一般的である。この安定化処理としては、活性化された触媒の外表面をワックス等により被覆して、空気との接触を遮断する方法、あるいは、活性化された触媒の外表面を軽度に酸化して酸化皮膜を形成し、空気との接触によるそれ以上の酸化を防止する方法などが挙げられる。この活性化され、安定化処理を施された触媒はそのままＦＴ合成反応に供することができる。 In addition, when the activation of the catalyst is performed in the facility for producing hydrocarbons by the FT synthesis method or the facility attached thereto, the activated catalyst is directly subjected to the FT synthesis reaction. On the other hand, for example, when the activation is performed in a catalyst production facility separated from the hydrocarbon production facility, a stabilization treatment is performed in order to prevent the catalyst from being deactivated due to contact with air during transportation or the like. Generally, it is shipped after being applied. As this stabilization treatment, the outer surface of the activated catalyst is coated with wax or the like to block contact with air, or the outer surface of the activated catalyst is lightly oxidized to form an oxide film. And a method for preventing further oxidation due to contact with air. This activated and stabilized catalyst can be directly used for the FT synthesis reaction.
以上のようにして得られる活性化されたＦＴ合成触媒を用いて、ＦＴ合成反応により炭化水素が製造される。この炭化水素の製造方法については、後に詳述する再生ＦＴ合成触媒を用いた場合と、使用する触媒が再生触媒であるか未使用の触媒であるかの点のみでの相違であるので、重複を避ける観点から説明を割愛する。 A hydrocarbon is produced by an FT synthesis reaction using the activated FT synthesis catalyst obtained as described above. This hydrocarbon production method is different from the case of using a regenerated FT synthesis catalyst, which will be described in detail later, and only whether the catalyst used is a regenerated catalyst or an unused catalyst. The explanation is omitted from the viewpoint of avoiding the problem.
ＦＴ合成反応に供された上記触媒は、反応時間の経過とともにその活性が低下する傾向にある。活性が未使用の触媒に比較して特定の範囲まで低下した触媒が、本実施形態の再生ＦＴ合成触媒の製造方法に係る使用済みＦＴ合成触媒となる。 The activity of the catalyst subjected to the FT synthesis reaction tends to decrease as the reaction time elapses. The catalyst whose activity is reduced to a specific range as compared with the unused catalyst becomes the used FT synthesis catalyst according to the method for producing the regenerated FT synthesis catalyst of the present embodiment.
再生を行なうための装置及び再生の形態には種々のものがある。ＦＴ合成反応を停止し、使用済みＦＴ合成触媒を上記反応装置内に収容したままの状態で再生を行なってもよい。あるいは、ＦＴ合成反応装置内の使用済みＦＴ合成触媒をＦＴ合成反応装置に接続された再生装置に移送し、該装置内にて再生を行なってもよい。この際、ＦＴ合成反応装置内の触媒の全てを移送して再生してもよいし、その一部を移送して再生してもよい。また、ＦＴ合成反応装置から抜き出した使用済みＦＴ合成触媒を、同装置とは独立した再生装置に移送し、再生を行なってもよい。この場合、抜き出された使用済みＦＴ合成触媒は空気に接触させないことが好ましい。抜き出した使用済みＦＴ合成触媒の空気との接触を遮断する観点からは、ＦＴ合成反応装置に接続された再生装置に移送して再生を行なうことが好ましい。 There are various types of playback apparatuses and playback modes. The FT synthesis reaction may be stopped and the regeneration may be performed while the used FT synthesis catalyst is housed in the reactor. Alternatively, the used FT synthesis catalyst in the FT synthesis reaction apparatus may be transferred to a regeneration apparatus connected to the FT synthesis reaction apparatus, and regeneration may be performed in the apparatus. At this time, all of the catalyst in the FT synthesis reaction apparatus may be transferred and regenerated, or a part thereof may be transferred and regenerated. Further, the used FT synthesis catalyst extracted from the FT synthesis reaction apparatus may be transferred to a regeneration apparatus independent of the apparatus for regeneration. In this case, it is preferable that the used FT synthesis catalyst extracted is not brought into contact with air. From the viewpoint of blocking the contact of the extracted used FT synthesis catalyst with the air, it is preferable to perform regeneration by transferring it to a regenerator connected to the FT synthesis reaction apparatus.
使用済みＦＴ合成触媒のうち、本発明の適用に適した触媒は、初期一酸化炭素転化率で表される活性が、相当する未使用の触媒の当該活性を基準として４０〜９５％、好ましくは５０〜９０％である使用済みＦＴ合成触媒である。なお、ここで、初期一酸化炭素転化率とは、所定の反応条件において実施されるＦＴ合成反応における一酸化炭素の反応開始から２．５時間経過した時に得られた一酸化炭素転化率をいう。また、基準とする「相当する未使用の触媒の当該活性」とは、相当する未使用の触媒（ＦＴ合成反応に使用される前のＦＴ合成触媒）について、上記使用済みＦＴ合成触媒について行なったものと同一条件でのＦＴ合成反応における初期一酸化炭素転化率をいう。また、以後、〔使用済みＦＴ合成触媒の初期一酸化炭素転化率／相当する未使用の触媒の初期一酸化炭素転化率〕（％）を「活性保持率」と呼ぶこととする。 Among the used FT synthesis catalysts, a catalyst suitable for application of the present invention has an activity represented by an initial carbon monoxide conversion of 40 to 95% based on the activity of the corresponding unused catalyst, preferably It is a used FT synthesis catalyst which is 50 to 90%. Here, the initial carbon monoxide conversion rate refers to the carbon monoxide conversion rate obtained when 2.5 hours have elapsed from the start of the reaction of carbon monoxide in the FT synthesis reaction carried out under predetermined reaction conditions. . In addition, “the corresponding activity of the corresponding unused catalyst” as a reference is the same as the used FT synthesis catalyst for the corresponding unused catalyst (the FT synthesis catalyst before being used in the FT synthesis reaction). The initial carbon monoxide conversion rate in the FT synthesis reaction under the same conditions as those described above. Hereinafter, [initial carbon monoxide conversion rate of used FT synthesis catalyst / corresponding initial carbon monoxide conversion rate of unused catalyst] (%) will be referred to as “activity retention”.
活性保持率が９５％を超える使用済みＦＴ合成触媒については、再生することなく継続して使用可能な活性を未だ有しており、また、再生による活性向上の幅も限られていることから、再生の対象としないことが合理的である。一方、活性保持率が４０％未満である使用済みＦＴ合成触媒については、その活性低下がコーク堆積、活性金属原子−担体間での複合酸化物の形成など、複数の要因による可能性が高いため、本発明の方法が効果を奏して、再使用に供することができる程度に活性を回復させることが困難な傾向にある。 About the used FT synthesis catalyst whose activity retention rate exceeds 95%, it still has an activity that can be continuously used without being regenerated, and the range of activity improvement by regeneration is limited. It is reasonable not to be reclaimed. On the other hand, for a used FT synthesis catalyst having an activity retention rate of less than 40%, the decrease in activity is likely due to a plurality of factors such as coke deposition and formation of a composite oxide between the active metal atom and the support. The method of the present invention has an effect, and it tends to be difficult to restore the activity to such an extent that it can be reused.
ＦＴ合成反応装置から抜き出された使用済みＦＴ合成触媒には、ＦＴ合成反応の生成物である炭化水素化合物が付着している。この炭化水素化合物はワックス分を含むため、常温では固体である。この使用済みＦＴ合成触媒を本発明の再生ＦＴ合成触媒の製造方法に供して活性を十分に回復させるためには、まず触媒に付着した炭化水素化合物の除去、すなわち脱油を施すことが好ましい。 The used FT synthesis catalyst extracted from the FT synthesis reaction apparatus is attached with a hydrocarbon compound that is a product of the FT synthesis reaction. Since this hydrocarbon compound contains a wax component, it is solid at room temperature. In order to use this used FT synthesis catalyst in the method for producing a regenerated FT synthesis catalyst of the present invention to sufficiently recover the activity, it is preferable to first remove hydrocarbon compounds adhering to the catalyst, that is, deoil.
脱油工程としては、付着した炭化水素化合物を含む触媒を、硫黄化合物、窒素化合物、塩素化合物、アルカリ金属化合物等を含まないパラフィンを主成分とする炭化水素油により洗浄する方法が挙げられる。具体的には、沸点約４００℃以下のＦＴ合成法の生成油もしくは類似した構造を持つノルマルパラフィン類が、同工程での洗浄油として用いられる。洗浄時の温度、圧力は任意に決定されるが、上記炭化水素油をその沸点近くの温度まで加熱し、洗浄を行なうとより洗浄の効果は大きい。脱油工程に使用する装置としては、オートクレーブ型容器、流通式反応器型容器などを用いることができる。脱油工程においては、脱油前の触媒に含まれる油分（炭素分質量換算）の７０質量％以上が除去されることが好ましい。この除去率が７０質量％を下回る場合は、スチーミング工程における水蒸気の触媒担体中の細孔内分散が十分でなく、活性の回復が十分とならない傾向にある。 Examples of the deoiling step include a method in which a catalyst containing an attached hydrocarbon compound is washed with a hydrocarbon oil mainly composed of paraffin that does not contain a sulfur compound, a nitrogen compound, a chlorine compound, an alkali metal compound, or the like. Specifically, a product oil of a FT synthesis method having a boiling point of about 400 ° C. or less or a normal paraffin having a similar structure is used as a cleaning oil in the same step. Although the temperature and pressure at the time of washing are arbitrarily determined, the washing effect is greater when the hydrocarbon oil is heated to a temperature near its boiling point and washed. As an apparatus used for the deoiling step, an autoclave type container, a flow reactor type container, or the like can be used. In the deoiling step, it is preferable that 70% by mass or more of the oil (in terms of carbon content) contained in the catalyst before deoiling is removed. When this removal rate is less than 70% by mass, the dispersion of water vapor in the catalyst support in the steaming process is not sufficient and the recovery of activity tends not to be sufficient.
本実施形態に係るスチーミング工程においては、水蒸気及び不活性ガスを含む混合気体に、上記脱油工程を経た使用済みＦＴ合成触媒を接触させる。上記混合気体中の水蒸気濃度は１〜３０体積％であり、好ましくは５〜２０体積％である。上記水蒸気濃度が１体積％未満の場合は、十分な活性回復の効果が得られない傾向となる。一方、水蒸気濃度が３０体積％を超える場合は、活性金属の過剰な凝集及びシリカを含む担体の構造崩壊を生じる傾向となるため、好ましくない。上記不活性ガスとしては窒素ガス等が挙げられる。上記混合気体中には、更に分子状水素又は一酸化炭素を含んでもよい。但し、分子状水素と一酸化炭素の両方を含むことは、ＦＴ合成反応が生起され、反応熱による温度上昇の懸念があることから好ましくない。 In the steaming process according to the present embodiment, the used FT synthesis catalyst that has undergone the deoiling process is brought into contact with a mixed gas containing water vapor and an inert gas. The water vapor concentration in the mixed gas is 1 to 30% by volume, preferably 5 to 20% by volume. When the water vapor concentration is less than 1% by volume, a sufficient activity recovery effect tends not to be obtained. On the other hand, when the water vapor concentration exceeds 30% by volume, it tends to cause excessive aggregation of the active metal and structural collapse of the support containing silica, which is not preferable. Nitrogen gas etc. are mentioned as said inert gas. The mixed gas may further contain molecular hydrogen or carbon monoxide. However, inclusion of both molecular hydrogen and carbon monoxide is not preferable because an FT synthesis reaction occurs and there is a concern of temperature increase due to reaction heat.
上記スチーミング工程における温度は、１５０〜３５０℃であり、好ましくは１７０〜２５０℃である。上記温度が１５０℃を下回る場合、活性回復の効果が得られにくい傾向にある。一方、上記温度が３５０℃を超える場合には、スチーミングに伴う酸化作用により活性金属原子の酸化が進行し、一酸化炭素転換に対する不活性種が生成するために好ましくない。 The temperature in the said steaming process is 150-350 degreeC, Preferably it is 170-250 degreeC. When the said temperature is less than 150 degreeC, it exists in the tendency for the effect of activity recovery to be hard to be acquired. On the other hand, when the temperature exceeds 350 ° C., oxidation of the active metal atom proceeds due to the oxidizing action accompanying steaming, and an inactive species for carbon monoxide conversion is generated, which is not preferable.
上記スチーミング工程における圧力は、大気圧〜５ＭＰａであり、大気圧〜３ＭＰａが好ましい。圧力が５ＭＰａを超える場合、活性回復の効果に比較してシリカを含む担体構造の崩壊の好ましくない影響が勝ることから好ましくない。 The pressure in the steaming step is from atmospheric pressure to 5 MPa, and preferably from atmospheric pressure to 3 MPa. When the pressure exceeds 5 MPa, it is not preferable because the undesirable influence of the collapse of the support structure containing silica is superior to the effect of recovery of activity.
上記スチーミング工程における時間は、温度、使用する装置等の影響が大きく一概には規定されないが、０．１〜１０時間程度が選択される。 The time in the steaming step is largely unaffected by the temperature, the apparatus used, etc., and is not generally defined, but is selected from about 0.1 to 10 hours.
ＦＴ合成反応においては、分子状水素と一酸化炭素との反応から、炭化水素と同時に副生成物として水が多量に生成し、ＦＴ合成反応装置内には常に水蒸気が存在する。したがって、ＦＴ合成触媒は反応中常に水蒸気に晒されていることとなる。このような履歴を受けて活性が低下した使用済みＦＴ合成触媒に、上述のようなスチーミング工程を施すことによってその活性が回復することは、全く予想外のことであった。 In the FT synthesis reaction, a large amount of water is produced as a by-product simultaneously with hydrocarbons from the reaction between molecular hydrogen and carbon monoxide, and water vapor is always present in the FT synthesis reaction apparatus. Therefore, the FT synthesis catalyst is always exposed to water vapor during the reaction. It was completely unexpected that the activity was recovered by performing the above-described steaming process on the used FT synthesis catalyst whose activity was lowered due to such a history.
以上のようにして、本実施形態に係る再生ＦＴ合成触媒を得ることができる。この再生ＦＴ合成触媒は、このままＦＴ合成反応に供することもできる。 As described above, the regenerated FT synthesis catalyst according to the present embodiment can be obtained. The regenerated FT synthesis catalyst can be used for the FT synthesis reaction as it is.
一方、本実施形態においては、スチーミング工程を経て得られた触媒に、分子状水素又は一酸化炭素を含む気体中で還元する還元工程を更に施して再生ＦＴ合成触媒を製造してもよい。スチーミング工程を経て得られた触媒においては、スチーミングによる弱い酸化作用により、活性金属原子の一部が金属から酸化物へと酸化されている傾向にある。当該触媒をＦＴ合成反応に供すると、この酸化物となった活性金属原子の少なくとも一部は、同反応の原料である分子状水素及び一酸化炭素の作用により、同反応中に還元されて金属となる。しかし、ＦＴ合成反応開始初期から、より高い活性金属原子の還元度（金属状態の活性金属原子／全活性金属原子（モル％））を確保し、より高い活性を発現させようとする場合には、上記還元工程を更に施すことが有効である。 On the other hand, in the present embodiment, a regenerated FT synthesis catalyst may be produced by further subjecting the catalyst obtained through the steaming step to a reduction step of reducing in a gas containing molecular hydrogen or carbon monoxide. In the catalyst obtained through the steaming process, a part of the active metal atoms tend to be oxidized from the metal to the oxide by the weak oxidizing action by the steaming. When the catalyst is subjected to an FT synthesis reaction, at least a part of the active metal atoms that have become oxides are reduced during the reaction by the action of molecular hydrogen and carbon monoxide, which are raw materials for the reaction, to form a metal. It becomes. However, from the beginning of the FT synthesis reaction, in order to secure a higher degree of reduction of active metal atoms (active metal atoms in metal state / total active metal atoms (mol%)) and to express higher activity It is effective to further perform the reduction step.
上記還元工程における雰囲気である分子状水素又は一酸化炭素を含む気体は特に限定されないが、水素ガス、水素ガスと窒素ガス等の不活性ガスとの混合気体、一酸化炭素及び一酸化炭素と窒素ガス等の不活性ガスとの混合気体などが挙げられる。上記気体が分子状水素を含まず、一酸化炭素を含むものである場合には、分子状水素による還元の場合に副生し、活性金属原子の還元を阻害すると推測される水の生成がないことから、より高い活性金属原子の還元度が得られる傾向にある。なお、上記気体が分子状水素と一酸化炭素とを共に含むものであると、還元工程においてＦＴ合成反応が生起され、反応熱による温度上昇等の懸念があることから、好ましくない。但し、それぞれの成分が微量混入したものである場合には許容される。 The gas containing molecular hydrogen or carbon monoxide that is the atmosphere in the reduction step is not particularly limited, but hydrogen gas, a mixed gas of hydrogen gas and inert gas such as nitrogen gas, carbon monoxide, carbon monoxide and nitrogen Examples thereof include a mixed gas with an inert gas such as a gas. When the gas does not contain molecular hydrogen and contains carbon monoxide, it is produced as a by-product in the case of reduction with molecular hydrogen, and there is no generation of water that is supposed to inhibit the reduction of active metal atoms. , Higher reduction of active metal atoms tends to be obtained. Note that it is not preferable that the gas contains both molecular hydrogen and carbon monoxide because an FT synthesis reaction occurs in the reduction step and there is a concern of temperature increase due to reaction heat. However, it is permissible if each component is a mixture of a small amount.
上記還元工程において、雰囲気として分子状水素を含む気体を用いる場合には、還元温度は２５０〜５００℃であることが好ましく、３５０〜４５０℃であることがより好ましい。還元温度が２５０℃よりも低い場合には、活性金属原子の還元度を高める効果が十分に得られない傾向にある。一方、還元温度が５００℃を超える場合には、活性金属の凝集が過剰に進行するため活性が低下する傾向にある。 In the reduction step, when a gas containing molecular hydrogen is used as the atmosphere, the reduction temperature is preferably 250 to 500 ° C, and more preferably 350 to 450 ° C. When the reduction temperature is lower than 250 ° C., the effect of increasing the reduction degree of the active metal atom tends to be insufficient. On the other hand, when the reduction temperature exceeds 500 ° C., the activity tends to decrease because the aggregation of the active metal proceeds excessively.
上記還元工程において、雰囲気として一酸化炭素を含む気体を用いる場合には、還元温度は２００〜４００℃であることが好ましく、２５０〜３５０℃であることがより好ましい。上記温度が２００℃よりも低い場合には、活性金属原子の十分な還元度が得られ難い傾向にある。一方、４００℃を超える場合には、一酸化炭素からカーボンナノチューブを代表とするカーボンを生成しやすい傾向にある。 In the reduction step, when a gas containing carbon monoxide is used as the atmosphere, the reduction temperature is preferably 200 to 400 ° C, and more preferably 250 to 350 ° C. When the said temperature is lower than 200 degreeC, it exists in the tendency for sufficient reduction | restoration degree of an active metal atom to be hard to be obtained. On the other hand, when the temperature exceeds 400 ° C., carbon typified by carbon nanotubes tends to be easily generated from carbon monoxide.
上記還元工程において、雰囲気の圧力は特に制限されないが、一般に大気圧〜５ＭＰａ程度である。また、還元時間は還元温度、使用する装置等に大きく依存することから一概に規定することは困難であるが、一般的に０．５〜３０時間程度である。 In the reduction step, the atmospheric pressure is not particularly limited, but is generally about atmospheric pressure to 5 MPa. Further, the reduction time largely depends on the reduction temperature, the apparatus to be used, and the like, and thus it is difficult to define it unconditionally.
以上のようにして、本実施形態に係る再生ＦＴ合成触媒が得られる。なお、上述の未使用のＦＴ合成触媒についての説明において述べたものと同様に、再生ＦＴ合成触媒においても、活性化状態にある触媒について空気との接触を伴う移送等を行う必要がある場合には、未使用の触媒に対するものと同様の安定化処理を施した上で、移送等を行うことが好ましい。なお、以後、〔再生ＦＴ合成触媒の初期一酸化炭素転化率／相当する未使用の触媒の初期一酸化炭素転化率〕（％）を「活性回復率」と呼ぶこととする。 As described above, the regenerated FT synthesis catalyst according to this embodiment is obtained. In the same way as described in the description of the unused FT synthesis catalyst, the regenerated FT synthesis catalyst also needs to be transported with contact with air for the catalyst in the activated state. It is preferable to carry out the transfer or the like after performing the same stabilization treatment as that for the unused catalyst. Hereinafter, [initial carbon monoxide conversion rate of regenerated FT synthesis catalyst / corresponding initial carbon monoxide conversion rate of unused catalyst] (%) will be referred to as “activity recovery rate”.
次に、本実施形態に係る再生ＦＴ合成触媒を用いて、一酸化炭素と水素ガスとを原料として、ＦＴ合成反応により炭化水素を製造する方法について説明する。上記炭化水素の製造方法としては特に限定されず、公知の方法を採用することができる。反応装置としては、固定床反応装置又はスラリー床反応装置が好ましい。また、原料である一酸化炭素の転化率を５０％以上とする条件下に反応が行われることが好ましく、７０〜９０％の範囲で行われることが更に好ましい。なお、触媒として再生された触媒を使用すること以外は、未使用の触媒を使用する場合と、基本的に相違はない。 Next, a method for producing hydrocarbons by FT synthesis reaction using carbon monoxide and hydrogen gas as raw materials using the regenerated FT synthesis catalyst according to the present embodiment will be described. It does not specifically limit as a manufacturing method of the said hydrocarbon, A well-known method is employable. As the reaction apparatus, a fixed bed reaction apparatus or a slurry bed reaction apparatus is preferable. Further, the reaction is preferably performed under the condition that the conversion rate of carbon monoxide as a raw material is 50% or more, and more preferably in the range of 70 to 90%. Note that there is basically no difference from the case of using an unused catalyst except that a regenerated catalyst is used as the catalyst.
以下、スラリー床型の反応装置を使用した例に沿って、本実施形態に係るＦＴ合成触媒を用いた炭化水素の製造方法について説明する。 Hereinafter, a method for producing hydrocarbons using the FT synthesis catalyst according to the present embodiment will be described along with an example using a slurry bed type reactor.
反応装置としては、例えば気泡塔型流動床反応装置が使用できる。気泡塔型流動床反応装置内には、反応温度において液状である炭化水素（通常は同反応装置で製造されるＦＴ合成炭化水素）に、本実施形態に係る再生ＦＴ合成触媒を懸濁させたスラリーが収容されており、ここへ反応塔下部より一酸化炭素ガス及び水素ガスの混合ガス（一般的には天然ガス等の炭化水素のリフォーミングにより得られる合成ガス）が導入される。上記混合ガスは反応塔内を気泡となって上昇する間に上記炭化水素中に溶解し、触媒と接触することにより炭化水素が生成する。また、上記混合ガスの気泡の上昇によりスラリーが攪拌され、流動状態が保たれる。上記反応塔内には反応熱を除去するための冷却媒体が内部を流通する冷却管が設置されており、熱交換により反応熱が除去される。 As the reaction apparatus, for example, a bubble column type fluidized bed reaction apparatus can be used. In the bubble column type fluidized bed reactor, the regenerated FT synthesis catalyst according to the present embodiment is suspended in hydrocarbon that is liquid at the reaction temperature (usually FT synthesized hydrocarbon produced in the reactor). A slurry is accommodated, and a mixed gas of carbon monoxide gas and hydrogen gas (generally a synthetic gas obtained by reforming a hydrocarbon such as natural gas) is introduced into the bottom of the reaction tower. The mixed gas dissolves in the hydrocarbons while rising in the form of bubbles in the reaction tower and comes into contact with the catalyst to generate hydrocarbons. Moreover, the slurry is stirred by the rising of the bubbles of the mixed gas, and the fluid state is maintained. A cooling pipe through which a cooling medium for removing reaction heat flows is installed in the reaction tower, and the reaction heat is removed by heat exchange.
ＦＴ合成反応の反応温度は、目標とする一酸化炭素転化率により定めることができるが、１５０〜３００℃であることが好ましく、１７０〜２５０℃であることがより好ましい。 The reaction temperature of the FT synthesis reaction can be determined by the target carbon monoxide conversion, but is preferably 150 to 300 ° C, more preferably 170 to 250 ° C.
反応圧力は０．５〜５．０ＭＰａであることが好ましく、２．０〜４．０ＭＰａであることがより好ましい。反応圧力が０．５ＭＰａ未満である場合は、一酸化炭素転化率が５０％以上になりにくい傾向があり、５．０ＭＰａを超えると、局所的な発熱を生じやすくなる傾向にあるので好ましくない。 The reaction pressure is preferably 0.5 to 5.0 MPa, and more preferably 2.0 to 4.0 MPa. If the reaction pressure is less than 0.5 MPa, the carbon monoxide conversion tends to be difficult to be 50% or more, and if it exceeds 5.0 MPa, local heat generation tends to occur, which is not preferable.
原料ガス中の分子状水素／一酸化炭素の比率（モル比）は０．５〜４．０であることが好ましく、１．０〜２．５であることがより好ましい。上記モル比が０．５未満の場合には反応温度が高くなり触媒が失活する傾向にあり、４．０を超える場合には、望ましくない副生成物であるメタンの生成量が増加する傾向にある。 The molecular hydrogen / carbon monoxide ratio (molar ratio) in the raw material gas is preferably 0.5 to 4.0, and more preferably 1.0 to 2.5. When the molar ratio is less than 0.5, the reaction temperature tends to be high and the catalyst tends to be deactivated. When it exceeds 4.0, the amount of methane that is an undesirable by-product tends to increase. It is in.
原料ガスのガス空間速度は５００〜５０００ｈ−１であることが好ましく、１０００〜２５００ｈ−１であることがより好ましい。ガス空間速度が５００ｈ−１未満の場合には、同一触媒量に対する生産性が低く、５０００ｈ−１を超える場合には、一酸化炭素の転化率が５０％以上になり難いため好ましくない。 Preferably the gas hourly space velocity of the raw material gas is 500~5000h -1, and more preferably 1000~2500h -1. If the gas space velocity is less than 500h -1, the low productivity for the same amount of catalyst, if more than 5000h -1, the conversion of carbon monoxide is not preferred since it is difficult it becomes 50% or more.
本実施形態に係る再生ＦＴ合成触媒は高い活性回復率を有している。また、上記再生ＦＴ合成触媒は高い連鎖成長確率（α）を有しており、この触媒を用いることにより、高い収率にてワックス留分、中間留分（灯軽油留分）、ナフサ留分に相当するノルマルパラフィンを主成分とする炭化水素、及び少量のガス状の炭化水素を得ることができる。特にワックス留分及び中間留分に富む炭化水素を高い収率で得ることができる。 The regenerated FT synthesis catalyst according to this embodiment has a high activity recovery rate. The regenerated FT synthesis catalyst has a high chain growth probability (α). By using this catalyst, wax fraction, middle fraction (kerosene oil fraction), naphtha fraction can be obtained with high yield. It is possible to obtain a hydrocarbon mainly composed of normal paraffin and a small amount of gaseous hydrocarbon. In particular, a hydrocarbon rich in wax fraction and middle fraction can be obtained in high yield.
本発明は上記好ましい実施形態に限定されることはなく、本発明の主旨を逸脱しない範囲で、適宜変更を加えることができる。 The present invention is not limited to the preferred embodiments described above, and appropriate modifications can be made without departing from the spirit of the present invention.
以下、実施例及び比較例に基づき本発明を更に具体的に説明するが、本発明は以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.
（実施例１）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が９２．３％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１１．２ｎｍ、ＺｒＯ２担持量８．５質量％（触媒の質量基準））２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素ガス＝９．８／９０．２の混合気体流通下、全圧１．５ＭＰａ、２００℃で１時間スチーミングを行った（スチーミング工程）。続いて、同反応装置内にて、水素気流下、４００℃で３時間還元を行った（還元工程）。これにより、再生ＦＴ合成触媒を得た。
Example 1
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention of 92.3% measured by the method described below, and is a deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 11.2 nm, ZrO 2 ) 25 g of a supported amount of 8.5% by mass (based on the mass of the catalyst) was charged into a fixed bed flow type reactor, and all the components were mixed under a mixed gas flow of water vapor / nitrogen gas = 9.8 / 90.2 by volume ratio. Steaming was performed for 1 hour at a pressure of 1.5 MPa and 200 ° C. (steaming process). Subsequently, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus (reduction step). Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
上記により得られた再生ＦＴ合成触媒５ｇを、窒素ガス雰囲気下にてセタン３０ｍｌと共に内容積１００ｍｌのオートクレーブに移し、ＦＴ合成反応を行った。水素ガス／一酸化炭素が２／１（モル比）の混合ガスを原料とし、Ｗ（触媒質量）／Ｆ（合成ガス流量）＝３ｇ・ｈ／ｍｏｌ、温度２３０℃、圧力２．３ＭＰａ、攪拌速度８００ｒｐｍにおいて反応を開始した。反応部出口のガス組成をガスクロマトグラフィー法により経時的に分析し、この分析データから前述の初期一酸化炭素転化率を算出した。また、生成物の分析から、連鎖成長確率αを常法により求めた。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行ない、初期一酸化炭素転化率を同様に求めた。そして、前述の定義に従って、使用済みＦＴ合成触媒の活性保持率、及び再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
5 g of the regenerated FT synthesis catalyst obtained above was transferred to an autoclave having an internal volume of 100 ml together with 30 ml of cetane under a nitrogen gas atmosphere to carry out an FT synthesis reaction. Using a mixed gas of hydrogen gas / carbon monoxide 2/1 (molar ratio) as a raw material, W (catalyst mass) / F (synthesis gas flow rate) = 3 g · h / mol, temperature 230 ° C., pressure 2.3 MPa, stirring The reaction was started at a speed of 800 rpm. The gas composition at the outlet of the reaction section was analyzed over time by a gas chromatography method, and the above-described initial carbon monoxide conversion was calculated from the analysis data. Further, from the analysis of the product, the chain growth probability α was determined by a conventional method. Separately, using the corresponding used FT synthesis catalyst and the corresponding unused catalyst, the FT synthesis reaction was carried out in the same manner as described above, and the initial carbon monoxide conversion was similarly determined. And according to the above-mentioned definition, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（実施例２）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が５０．１質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１２．４ｎｍ、ＺｒＯ２担持量７．９質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素ガス＝１１．２／８８．８の混合気体流通下、全圧１．６ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 2)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention of 50.1% by mass, measured by the method described below, and a deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 12.4 nm, ZrO 2 loading (7.9% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen gas = 11.2 / 88.8 by volume ratio, the total pressure was 1.6 MPa, Steaming was performed at 200 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例３）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７８．４質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径２０．４ｎｍ、ＺｒＯ２担持量６．６質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝９．４／９０．６の混合ガス流通下、全圧０．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 3)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 78.4% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 20.4 nm, ZrO 2 supported amount 6.6 mass%) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 9.4 / 90.6 in volume ratio, total pressure 0.5 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例４）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７７．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径８．９ｎｍ、ＺｒＯ２担持量７．１質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝８．２／９１．８の混合ガス流通下、全圧０．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
Example 4
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described below of 77.2% by mass, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 8.9 nm, ZrO 2 loading (7.1% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 8.2 / 91.8 in volume ratio, total pressure 0.5 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例５）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７１．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１８．４ｎｍ、ＺｒＯ２担持量９．４質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝６．５／９３．５の混合ガス流通下、全圧１．６ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 5)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 71.2% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 18.4 nm, ZrO 2 loading (9.4% by mass) was charged in a fixed bed flow reactor and the total pressure was 1.6 MPa, 200 under a mixed gas flow of water vapor / nitrogen = 6.5 / 93.5 in volume ratio. Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例６）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７１．１質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１７．６ｎｍ、ＺｒＯ２担持量２．６質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝７．４／９２．６の混合ガス流通下、全圧１．６ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 6)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 71.1% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 17.6 nm, ZrO 2 loading (2.6% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 7.4 / 92.6 in volume ratio, total pressure 1.6 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例７）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７６．６質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１４．３ｎｍ、ＺｒＯ２担持量７．１質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝２７．１／７２．９の混合ガス流通下、全圧２．３ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 7)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 76.6% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter: 14.3 nm, ZrO 2 loading (7.1% by mass) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 27.1 / 72.9 by volume ratio, the total pressure was 2.3 MPa, 200 μm. Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例８）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７４．５質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１５．２ｎｍ、ＺｒＯ２担持量６．６質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝４．４／９５．６の混合ガス流通下、全圧２．２ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 8)
<Preparation of regenerated FT synthesis catalyst>
The activity retention measured by the method described later is 74.5% by mass, and is used in the FT synthesis reaction and deoiled in powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 15.2 nm, ZrO 2 supported amount 6.6% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 4.4 / 95.6 by volume ratio, total pressure 2.2 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例９）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７２．３質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１０．２ｎｍ、ＺｒＯ２担持量２．３質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝１０．５／８９．５の混合ガス流通下、全圧２．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
Example 9
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described later of 72.3% by mass, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 10.2 nm, ZrO 2 loading amount 2.3 mass%) was charged in a fixed bed flow reactor and the total pressure was 2.5 MPa, 200 under a mixed gas flow of water vapor / nitrogen = 10.5 / 89.5 by volume ratio. Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例１０）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７２．８質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１０．９ｎｍ、ＺｒＯ２担持量３．８質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝１１．４／８８．６の混合ガス流通下、全圧０．１ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 10)
<Preparation of regenerated FT synthesis catalyst>
The activity retention measured by the method described later is 72.8% by mass, and is used in the FT synthesis reaction and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 10.9 nm, ZrO 2 supported amount 3.8% by mass) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 11.4 / 88.6 in volume ratio, total pressure 0.1 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例１１）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７６．４質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１６．４ｎｍ、ＺｒＯ２担持量５．１質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝８．８／９１．２の混合ガス流通下、全圧２．２ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 11)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described below of 76.4% by mass, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 16.4 nm, ZrO 2 loading (5.1% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 8.8 / 91.2 in volume ratio, total pressure 2.2 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例１２）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７７．４質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１６．９ｎｍ、ＺｒＯ２担持量４．７質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝７．６／９２．４の混合ガス流通下、全圧２．１ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 12)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 77.4% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 16.9 nm, ZrO 2 loading (4.7% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 7.6 / 92.4 in volume ratio, total pressure 2.1 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例１３）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７６．４質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１８．４ｎｍ、ＺｒＯ２担持量１３．２質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝８．８／９１．２の混合ガス流通下、全圧１．６ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 13)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 76.4% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 18.4 nm, ZrO 2 supported amount 13.2% by mass) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 8.8 / 91.2 by volume ratio, total pressure 1.6 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（実施例１４）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７７．１質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１７．６ｎｍ、ＺｒＯ２担持量０．７質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝７．６／９２．４の混合ガス流通下、全圧１．６ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Example 14)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described below of 77.1% by mass, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 17.6 nm, ZrO 2 loading amount 0.7 mass%) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 7.6 / 92.4 by volume ratio, total pressure 1.6 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率、及び再生ＦＴ合成触媒を使用した場合の連鎖成長確率αを算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Similarly to Example 1, the activity retention rate of the used FT synthesis catalyst, the activity recovery rate of the regenerated FT synthesis catalyst, and the chain growth probability α when the regenerated FT synthesis catalyst was used were calculated. The results are shown in Table 1.
（比較例１）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が３５．８質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１２．４ｎｍ、ＺｒＯ２担持量８．２質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝１１．２／８８．８の混合ガス流通下、全圧１．６ＭＰａ、２１０℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 1)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention rate of 35.8% by mass, measured by the method described later, and a deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 12.4 nm, ZrO 2 loading (8.2% by mass) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 11.2 / 88.8 in a volume ratio, the total pressure was 1.6 MPa, 210 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例２）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７５．３質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１４．３ｎｍ、ＺｒＯ２担持量７．１質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝４１／５９の混合ガス流通下、全圧２．３ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 2)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention of 75.3% by mass measured by the method described below, and used in a deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter of 14.3 nm, ZrO 2 loading (7.1% by mass) was charged in a fixed bed flow type reaction apparatus, and under a mixed gas flow of water vapor / nitrogen = 41/59 by volume ratio, the total pressure was 2.3 MPa and 200 ° C. for 1 hour. Steamed. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例３）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７４．１質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１５．２ｎｍ、ＺｒＯ２担持量６．６質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝０．４／９９．６の混合ガス流通下、全圧２．２ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 3)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 74.1% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 15.2 nm, ZrO2 loading (6.6 mass%) (25 g) was charged into a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 0.4 / 99.6 in volume ratio, total pressure 2.2 MPa, 200 ° C. And steamed for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例４）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７０．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１０．９ｎｍ、ＺｒＯ２担持量３．８質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝１１．４／８８．６の混合ガス流通下、全圧５．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 4)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 70.2% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 10.9 nm, ZrO2 loading (3.8% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 11.4 / 88.6 in volume ratio, total pressure 5.5 MPa, 200 ° C. And steamed for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例５）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７５．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１２．３ｎｍ、ＺｒＯ２担持量６．３質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝４．４／９５．６の混合ガス流通下、全圧２．２ＭＰａ、３６２℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 5)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described below of 75.2% by mass, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 12.3 nm, ZrO 2 loading (6.3% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 4.4 / 95.6 in volume ratio, total pressure 2.2 MPa, 362 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例６）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７５．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径１４．３ｎｍ、ＺｒＯ２担持量５．４質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝４．４／９５．６の混合ガス流通下、全圧２．１ＭＰａ、１２１℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 6)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described later of 75.2% by mass and deoiled in the form of a powdered Co / SiO 2 —ZrO 2 catalyst (average pore diameter of 14.3 nm, ZrO 2 loading (5.4% by mass) (25 g) was charged into a fixed bed flow reactor and the total pressure was 2.1 MPa, 121 under a mixed gas flow of water vapor / nitrogen = 4.4 / 95.6 in volume ratio. Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例７）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７５．３質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径２７．２ｎｍ、ＺｒＯ２担持量６．６質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝９．４／９０．６の混合ガス流通下、全圧０．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 7)
<Preparation of regenerated FT synthesis catalyst>
Used in the FT synthesis reaction having an activity retention measured by the method described later of 75.3% by mass and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore diameter 27.2 nm, ZrO 2 supported amount 6.6 mass%) was charged in a fixed bed flow reactor, and under a mixed gas flow of water vapor / nitrogen = 9.4 / 90.6 in volume ratio, total pressure 0.5 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
（比較例８）
＜再生ＦＴ合成触媒の調製＞
後述の方法で測定した活性保持率が７４．２質量％である、ＦＴ合成反応に使用済みであり、脱油された粉体状Ｃｏ／ＳｉＯ２−ＺｒＯ２触媒（平均細孔径３．３ｎｍ、ＺｒＯ２担持量７．１質量％）２５ｇを、固定床流通式反応装置に充填し、体積比で水蒸気／窒素＝８．２／９１．８の混合ガス流通下、全圧０．５ＭＰａ、２００℃で１時間スチーミングを行った。次に、同反応装置内にて、水素気流下、４００℃で３時間還元を行った。これにより、再生ＦＴ合成触媒を得た。
(Comparative Example 8)
<Preparation of regenerated FT synthesis catalyst>
An activity retention measured by the method described later is 74.2% by mass, used in the FT synthesis reaction, and deoiled powdery Co / SiO 2 —ZrO 2 catalyst (average pore size 3.3 nm, ZrO 2 loading (7.1% by mass) was charged in a fixed bed flow type reactor, and under a mixed gas flow of water vapor / nitrogen = 8.2 / 91.8 in volume ratio, total pressure 0.5 MPa, 200 Steaming was performed at 1 ° C. for 1 hour. Next, reduction was performed at 400 ° C. for 3 hours in a hydrogen stream in the same reaction apparatus. Thereby, a regenerated FT synthesis catalyst was obtained.
＜ＦＴ合成反応評価＞
触媒として上記により得られた再生ＦＴ合成触媒を用いた以外は実施例１と同様の操作にてＦＴ合成反応を行なった。また、別途、相当する使用済みＦＴ合成触媒及び相当する未使用の触媒を用いて、上記と同様の方法でＦＴ合成反応を行なった。そして、実施例１と同様に、使用済みＦＴ合成触媒の活性保持率、再生ＦＴ合成触媒の活性回復率を算出した。結果を表１に示す。
<FT synthesis reaction evaluation>
The FT synthesis reaction was performed in the same manner as in Example 1 except that the regenerated FT synthesis catalyst obtained above was used as the catalyst. Separately, an FT synthesis reaction was performed in the same manner as described above using a corresponding used FT synthesis catalyst and a corresponding unused catalyst. Then, as in Example 1, the activity retention rate of the used FT synthesis catalyst and the activity recovery rate of the regenerated FT synthesis catalyst were calculated. The results are shown in Table 1.
Claims (4)
シリカを含む担体にコバルトが担持され、初期一酸化炭素転化率で表される活性が、相当する未使用の触媒の当該活性を基準として４０〜９５％である前記使用済み触媒を、大気圧〜５ＭＰａの圧力、１５０〜３５０℃の温度にて、１〜３０体積％の水蒸気及び不活性ガスを含む混合ガスに接触させるスチーミング工程を備え、
前記シリカを含む担体は、窒素吸着法による平均細孔径が４〜２５ｎｍであり、
前記シリカを含む担体が、更に触媒の質量を基準として１〜１０質量％の酸化ジルコニウムを含む、
ことを特徴とする再生フィッシャー・トロプシュ合成触媒の製造方法。 A method for producing a regenerated Fischer-Tropsch synthesis catalyst obtained by regenerating a spent catalyst used in a Fischer-Tropsch synthesis reaction,
Are cobalt is supported on a support comprising silica, initial carbon monoxide activity represented by the conversion of the corresponding 40% to 95% in the spent catalyst is the activity of fresh catalyst as a reference, atmospheric pressure A steaming step of contacting a mixed gas containing 1 to 30% by volume of water vapor and an inert gas at a pressure of ˜5 MPa and a temperature of 150 to 350 ° C .;
Support containing the silica has an average pore diameter by nitrogen adsorption method Ri 4~25nm der,
The silica-containing support further contains 1 to 10% by mass of zirconium oxide based on the mass of the catalyst .
A method for producing a regenerated Fischer-Tropsch synthesis catalyst characterized by the above.
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| RU2012142320/04A RU2549569C2 (en) | 2010-03-05 | 2011-02-14 | Method for manufacturing regenerated fischer-tropsch synthesis catalyst and hydrocarbon manufacturing method |
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| MYPI2012700602A MY156577A (en) | 2010-03-05 | 2011-02-14 | Method for manufacturing a regenerated fischer-tropsch synthesis catalyst, and hydrocarbon manufacturing method |
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| AU (1) | AU2011222198B2 (en) |
| CA (1) | CA2791270C (en) |
| MY (1) | MY156577A (en) |
| RU (1) | RU2549569C2 (en) |
| WO (1) | WO2011108348A1 (en) |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| MY160868A (en) * | 2010-03-05 | 2017-03-31 | Jx Nippon Oil & Energy Corp | Fischer-tropsch synthesis catalyst, manufacturing method therefor, and hydrocarbon manufacturing method |
| CN105903497B (en) * | 2016-05-24 | 2019-06-07 | 江南大学 | The regeneration treating method for the cobalt-base catalyst that F- T synthesis uses |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110449B1 (en) * | 1982-11-22 | 1986-08-13 | Shell Internationale Researchmaatschappij B.V. | Process for the preparation of a fischer-tropsch catalyst, a catalyst so prepared and use of this catalyst in the preparation of hydrocarbons |
| GB9010075D0 (en) | 1990-05-04 | 1990-06-27 | Shell Int Research | Process for the preparation of alumina based extrudates |
| GB9117899D0 (en) * | 1991-08-20 | 1991-10-09 | Shell Int Research | Process for the activation of a catalyst |
| US6486220B1 (en) * | 1999-11-17 | 2002-11-26 | Conoco Inc. | Regeneration procedure for Fischer-Tropsch catalyst |
| MXPA02012731A (en) * | 2000-07-03 | 2003-05-14 | Shell Int Research | Catalyst and process for the preparation of hydrocarbons. |
| US6531517B1 (en) * | 2000-08-01 | 2003-03-11 | Exxonmobil Research And Engineering Company | Process for increasing carbon monoxide hydrogenation activity of catalysts via low temperature oxidation with water, steam or mixture thereof |
| US6812179B2 (en) * | 2001-04-25 | 2004-11-02 | Syntroleum Corporation | Process for regenerating a slurry fischer-tropsch catalyst |
| US6787496B2 (en) * | 2002-01-29 | 2004-09-07 | Exxonmobil Research And Engineering Company | Supported catalyst treatment |
| US6878655B2 (en) * | 2002-09-20 | 2005-04-12 | Conocophillips Company | Method and apparatus for the regeneration of hydrocarbon synthesis catalysts |
| MY142111A (en) | 2004-04-16 | 2010-09-15 | Nippon Oil Corp | Catalyst for fischer-tropsch synthesis and process for producing hydrocarbons |
| JP2007270049A (en) * | 2006-03-31 | 2007-10-18 | Nippon Oil Corp | Method for producing hydrocarbon by reduction of carbon monoxide |
| JP4907212B2 (en) * | 2006-03-31 | 2012-03-28 | Ｊｘ日鉱日石エネルギー株式会社 | Carbon monoxide reduction catalyst and preparation method thereof |
| KR101430775B1 (en) | 2006-08-25 | 2014-08-18 | 신닛떼쯔 수미킨 엔지니어링 가부시끼가이샤 | Catalyst for producing hydrocarbon from synthetic gas, method for producing catalyst, method for regenerating catalyst, and method for producing hydrocarbon from synthetic gas |
| JP4808688B2 (en) * | 2006-08-25 | 2011-11-02 | 新日本製鐵株式会社 | Catalyst for producing hydrocarbons from synthesis gas, catalyst production method, catalyst regeneration method, and method for producing hydrocarbons from synthesis gas |
| EP1920836A1 (en) * | 2006-10-27 | 2008-05-14 | Shell Internationale Researchmaatschappij B.V. | Process for regenerating a cobalt catalyst |
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| WO2011108348A1 (en) | 2011-09-09 |
| AU2011222198A1 (en) | 2012-09-06 |
| CA2791270A1 (en) | 2011-09-09 |
| RU2012142320A (en) | 2014-04-10 |
| CN102791377A (en) | 2012-11-21 |
| US8557725B2 (en) | 2013-10-15 |
| CA2791270C (en) | 2018-04-03 |
| RU2549569C2 (en) | 2015-04-27 |
| CN102791377B (en) | 2015-02-25 |
| US20120322899A1 (en) | 2012-12-20 |
| MY156577A (en) | 2016-03-15 |
| AU2011222198B2 (en) | 2016-01-21 |
| ZA201207040B (en) | 2013-05-29 |
| JP2011183282A (en) | 2011-09-22 |
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